Detergent and emulsifying agent



Patented July 30, 1940 DETERGENT AND EMULSIFYING AGENT Fred WeaverMuncie, New Brunswick, N. 1., as-

signor to Colgate-Palmolive-Peet Company, Jersey City, N. J., acorporation of Delaware No Drawing.

Application May 13, 1937,

Serial No. 142,497

27 Claims.

This invention relates to derivatives of polyhydroxy alcohols. Itrelates more specifically to derivatives of these alcohols in which oneor more of the hydroxyls is replaced by an alkyl or acyl group and inwhich there is present in addition a residue of boric acid. Suchcompounds, according to this invention are then treated with asolubilizing agent such as a sulfating, sulfonating or phosphatingagent, if desired, to produce compounds that have cleansing, preserving,wetting and emulsifying action and are excellent detergents.

Examples of the poly-hydroxy alcohols that may be employed are ethyleneglycol, propylene glycol, glycerine, B-methyl glycerine, erythritol,diglycerol, poly-glycerols, sugar alcohols such as mannitol andsorbitol, sugar acids, reaction prodnets of the poly-hydroxy alcoholswith ethylene oxide and other poly-hydroxy compounds. In certain methodsof preparation, the chlorhydrin or glyclde derivatives of thepoly-hydroxy alcohols may be employed.

The alkyl group must contain at least eight carbon atoms and be attachedto the poly-hydroxy alcohol residue by an ether linkage. Such ethers arederived by known methods by reaction of the poly-hydroxy alcohol withalcohols straight chain or branched, and primary, secondary or tertiary.Such alcohols are those derived from fatty or other naturally occurringacids by reduction of the carboxyl group, from oleflns derived frompetroleum or other sources, by reduction of ke- *tones and by theoxidation of paraflin. Exam-- pies are lauryl alcohol, alcohols obtainedby the reduction of mixed fatty acids of coconut oil or tallow or theiresters, oleyl alcohol, di-caproyl alcohol, abietanol, montanol.

The acylgroup, likewise, must contain at least eight carbon atoms andmay be straight chain or branched. Examples are lauric, myristic, oleicor stearic acids, mixed fatty acids from coconut oil, palm oil, palmkernel oil, babasu nut oil, olive oil, tallow, rosin or abietic acid,montanic acid and acids from the oxidation of paraflin:

It is not known definitely in how many ways the boric acid may becombined with ethers or esters of these polyhydroxy compounds. Itappears, for instance. that ortho-boric acid may not only be combinedwith a compound containing one hydroxyl to yield a derivative of thetype:

with two hydroxyls to give a compound of the type:

o R/ mon but also that two or three linkages of the boric acid residuemay be attached to hydroxyls of separate and distinct organic residuesgiving a compound of the type:

where R, R or R." may represent either the same or different kinds ofradicals or residues. It is seen that the compounds formed according tothe invention may be quite complex and of high molecular weight, apossibility that may explain the excellent emulsifying action of thecompounds.

Similarly, by variation in operating conditions and choice ofsolubilizlng agent, it is possible to attach one or more than onesolubilizing group to the organic boron compound, and mixed derivativesmay be formed in which the boric acid residue links two or more alkyl oracyl poly-hydroxy derivatives, with the sulfate, phosphate or othersolubilizlng group occurring in ratio of one or less than one withrespect to the poly-hydroxy alcohol residue. Since the compounds formedmay be quite complex, it is not my intention to limit the invention byillustration with formulas, but only to the alkyl or acyl derivatives ofa poly-hydroxy compound in which the alkyl or acyl group contains notless than eightcarbon atoms, the derivatives containing a boric acidresidue 45 and if desired in addition a solubilizing group such as asulfuric acid, or phosphoric acid residue.

In the treatment with a sulfonating agent, an aromatic compound such asnaphthalene or phenol or cresol may be added in which case the ringcompound is inserted between the poly-hydroxy borate residue and thesulfuric acid residue, and a substituted aromatic sulfonate is formed.Or mixed ring compounds obtained by the liquid $02, or other knownmethod of extraction of a fraction of petroleum, particularly from GulfCoast or California crudes may be employed in place of aromaticcompounds of known structure. Also, olefins, such as decene, octadecene,isobutylene or its polymers, or other oleflns obtained by separationfrom or cracking of petroleum or a fraction of petroleum, may beintroduced with the ring compounds during sulfonation, these attachingthemselves to the ring as alkyl substituents.

Certain of the boric acid derivatives of alkyl or acyl derivatives ofpoly-hydroxy alcohols are water soluble, as for example the borates ofthe ethylene oxide derivatives of alkyl ethers or acyl esters ofsorbitol. Others form emulsions with water but for solubility in waterrequire the presence in the compound of a solubilizing group such assulfuric or phosphoric acid residue or an aromatic sulfonic group.

All of the sulfated compounds of the general class described above thathave been prepared are water soluble and possess marked wetting anddetergent properties. The alkali, alkaline earth and heavy metal saltsare water soluble. By variation in the choice of poly-hydroxy alcoholand the proportion of boric acid and conditions of its reaction, it ispossible to vary the emulsifying characteristics of the product formed.Furthermore, boric acid possesses a preservative action toward bacterialdecomposition and compounds of the' type described are quite solublederivatives of boric acid in a form that in aqueous solution haveexceptional penetrating power.

The un-sulfated boric acid esters are excellent emulsifying agents.

Borates of the poly-hydroxy alkyl or acyl derivatives are easilyprepared by heating them with ortho or meta-boric acid in the molalratio desired under a vacuum to promote removal of water. In addition,the acyl derivatives may be formed by reacting the preformedpoly-hydroxy borate with a fatty acid, or fatty oil.

Boro-sulfates of the alwl or acyl derivatives of poly-hydroxy alcoholsmay be prepared in several ways:

1. The poly-hydroxy alcohol may be reacted with orthoor metaboric acidunder conditions that cause removal of water of reaction and the alcoholborate treated with fatty alcohols or fatty acids or their glycerides orother esters in such a manner as to result in the formation of the corresponding ether or ester of the poly-hydroxy alcohol borate. Thecompound is then sulfated by suitable reagents, such as sulfuric acid,oleum, chlorsulfonic acid, SO: in liquid 80:. The order of introductionof the fatty acid or alcohol and sulfuric acid may be reversed.

2. The ether or ester derivatives of poly-hydroxy alcohols may beprepared by known methods and converted into boric acid derivativesunder conditions that result in the removal of water of reaction, afterwhich the compound may be sulfated by the reagents indicated in 1.

3. A mixture of fatty acid or its glyceride, the poly-hydroxy alcohol,boric acid or its anhydrlde and sulfuric acid or fuming sulfuric acidmay be heated to about 50 C. until the reaction product is entirelymiscible with water, attention being paid to proportioning theingredients in the molal relationship desired in the product, and withsulfuric acid of suflicient strength and quantity to form the sulfateand absorb the water of reaction. Sulfuric acid in'this case acts tohydrolyze the tri-glyceride if used, to esterify the poly-hydroxyalcohol with fatty acid present or formed by hydrolysis, to bring aboutester formation with the boric acid, to sulfate the compound and toabsorb the water of reaction.

Illustrative equations are given below. The equations are not intended,however, to limit the scope of the invention. More particularly, is itnot intended to limit the invention to compounds of the simple structureindicated. As discussed above, it is probable that more complexcompounds are formed by the attachment of more than one organic residueto a single boric acid residue, and specific claim is made to such com-P unds.

ROCHr-CH-CHCHCHCH| i. i. i. t. t. t J; e H: H: Ha Ha H:

a Ha Ha Ha H:

B6B) n 11 n The borate of the Dentahydroxyl ethyl ether of sorbitolfatty alcohol ether is soluble in water and exhibits marked emulsifying,wetting and detergent properties.

R-OCH,CHg-O-CHg-CHrBOg-i-Hfl) The meta-boric acid ester of the fattyether of di-ethylene glycol is an excellent emulsifying agent.

The boro-sulfate of fatty acid monc-glyceride is soluble in water andhas marked wetting, emulsifying and detergent properties in aqueoussolution. The salts exhibit the same properties.

The boro-sulfate of the fatty ether of glycerine is water soluble and assuch or in form of its alkali, alkaline earth, ammonium and organicamine salts exhibits marked emulsifyin wetting and detergentcharacteristics.

CHIOH C1110 O C R Neutralization may be carried out to form the mixedsalt of the organic compound and the excess sulfuric'acid.

It is specifically within the scope of this invention to produce andemploy as cleansing, preserving, wetting, deterging and emulsifyingagents, the bore-sulfuric acid derivatives as such or their compoundswith alkalies or alkaline earths, ammonia, an ethanolamine, or otherbasic substance, whether organic or inorganic.

EXAMPLES or PREPARATION 1.Coconut oil fatty acid monoglyceride borate94.7 gms. of coconut oil fatty acid monoglyceride and 6.9 gms. ofortho-boric acid were mixed in a distilling flask and warmed. Above 100C. water was evolved and at 125 0., solution of the The flask was placedunder vacuum to assist in withdrawal of water and the product heated to150 C. under 1" pressure. The loss in weight amounted to 6.5 gms.whereas theory. would require'6.0 gms. The product was a clear strawcolored liquid slowly solidifying at about 28 C. No boric acid separatedon standing.

2.Sulfation of coconut oil monoglyceride borate 43.0 gms. of coconut oilmonoglyceride borate prepared as above was warmed to 47 C. and 69.8 gms.of sulfuric acid (102.8%) was added dropwise. Within a short time afterthe acid had been added, a sample of the product was completely solublein water. The mixture of the organic boro-sulfuric acid with the excesssulfuric acid was stirred into ice water and neutralized with causticsoda. The product formed a perfectly clear 1% solution in water, whethersoft or hard, and exhibited excellent foaming, wetting and washingproperties.

3.Coconut oil fatty acid monoglycefide borosulfate 43.2 gms. of coconut01], 12.8 gms. of 99.3% glycerine, and 4.0 gms. of ortho-boric acid weretaken with 105.2 gms. of sulfuric acid. The sulfuric acid was of 102.84%strength, containing 11.9% of free $03. The boric acid was added to thesulfuric acid and the mixture placed in an ice bath, after which withstirring, the glycerine was added dropwise. The mixture was warmed to45-50 C. and at this temperature with stirring, the oil was addedslowly. After holding the batch at this. temperature for minutes, a testsample was perfectly clear on dilution with water. The batch was nowdumped into a mixture of ice and water and neutralized with 30% causticsoda.

4.Fatty acid hydrozyethyl sorbitol bm'ate sorbitol were converted intothe ortho-boric acid ester by heating in vacuo with 10.3 grams ofortho-boric acid until the water of reaction was removed.

5.-Boro-sulphate of launll glycerine ether 138 grams of the ether ofglycerine and lauryl alcohol were heated in vacuo with 28 grams ofmeta-boric acid at a temperature up to 150 C. until the reaction wascompleted by removal of the water liberated. The product was thentreated with 275 grams of 20% oleum H2804) at a temperature of 30 to C.for one hour. The reaction mixture was then poured into ice and waterand neutralized with monoethanolamine to a pH of 7.0.

6.-Boro-sulphonate of cocoanut oil monoglyceride and Edeleanu extract ofpetroleum 284 grams of the monoglyceride of cocoanut oil fatty acidswere converted into the orthobnric acid ester as described in Example 1.This was mixed with 100 grams of Edeleanu extract of Californialubricating oil and the whole treated with 500 grams of 20% oleum at 8C. for about 2 hours. The reaction mixture was then poured into ice andwater and neutralized with ammonium hydroxide.

7.Boro-sulphonate of cocoanut oil monoglyceride, olefin and naphthalene284 grams of cocoanut oil fatty acid monoglyceride were converted intothe meta-boric acid ester by heating in vacuo with 28 grams of metaboricacid. The product was mixed with 125 grams of naphthalene and 100 gramsof decene and heated at 75 C. with 500 grams of 20% oleum for 2 hours.The reaction mixture was then extracted with butyl alcohol and thealcoholic-solution neutralized with an aqueous solution of sodiumbicarbonate, after which the alcohol solution was removed bydistillation.

Having described my invention, 1 claim:

1. A process for preparing boric acid esters of fatty acidmonoglycerides which comprises heating at least one fatty acidmonoglyceride and boric acid under conditions to remove the water ofreaction.

2. The process which comprises preparing a boric acid ester of apolyhydroxy alcohol, condensing said ester with at least one compound ofthe class consisting of fatty alcohols, fatty acids, and esters thereof,to form a boric acid ester of a compound of the class consisting ofpartial ethers and esters of polyhydroxy alcohols, sulphating thecondensation product and neutralizing the resulting material.

3. The process which comprises preparing a boric acid ester of apolyhydroxy alcohol, treating said ester with a sulphating agent,condensing the product with at least one compound of the classconsisting of fatty alcohols, fatty acids and esters thereof, to form aninorganic acid ester of a compound of the class consisting oi partialethers and esters of polyhydroxy alcohols, and neutralizing theresulting inorganic acid ester.

4. The process which comprises reacting at least one compound of theclass consisting of partial ethers and esters of polyhydroxy alcohols,with boric acid to form the corresponding boric acid ester, sulphatingsaid boric acid ester and neutralizing the resulting product.

5. The process which comprises reacting a mixture of a polyhydroxyalcohol, boric acid, sulphuric acid, and a compound of the classconsisting of fatty acids and esters thereof by warming until thereaction product is miscible with water, and neutralizing the resultingproduct.

6. The process which comprises warming a mixture containing in molecularproportions about one part of coconut oil, about two parts ofsubstantially anhydrous glycerine, from about one to three parts ofboric acid, and more than three parts of sulphuric acid at from 30 to C.until the product is miscible with water, and neutralizing the reactionproduct.

7. The process of producing a wetting agent and detergent whichcomprises reacting at least one compound of the class consisting ofpartial ethers and esters of polyhydroxy alcohols, with boric acid, anaromatic compound, and fuming sulphuric acid.

8. The process of producing a wetting agent and detergent whichcomprises reacting an olefin and at least one compound of the classconsisting of partial ethers and esters of polyhydroxy alcohols, withboric acid, an aromatic compound, and fuming sulphuric acid.

9. The process of producing a wetting agent and detergent whichcomprises reacting boric acid and at least one compound of the classconsisting of partial ethers and esters of polyhydroxy alcohols, with aliquid sulphur dioxide extract of a fraction of petroleum, and fumingsulphuric acid.

10. The process which comprises reacting a partial ether of apolyhydroxy alcohol and a high molecular weight aliphatic alcohol, withboric acid under conditions to remove the water of reaction.

11. The process which comprises reacting a partial ester of apolyhydroxy alcohol and a high molecular weight fatty acid, with boricacid under conditions to remove the water of reaction.

12. The process which comprises reacting a mixed ether of a polyhydroxyalcohol and a high molecular weight aliphatic alcohol, with boric acid,and with a sulphonating agent.

13. The process which comprises reacting a partial ester of apolyhydroxy alcohol and a high molecular weight fatty acid, with boricacid, and with a sulphonating agent.

14. The process which comprises reacting a polyhydroxy alcohol with ahigh molecular weight fatty acid, and with boric acid under conditionsto remove the water of reaction.

15. The process which comprises reacting at least one high molecularweight aliphatic compound selected from the group consisting of partialethers and esters of polyhydroxy alcohols,

" with boric acid, and with a sulphonating agent.

16. A compound of the class consisting of boric acid esters, boricacid-sulphuric acid esters, boric acid-phosphoric acid esters, and saltsof said esters, of at least one compound of the class consisting ofaliphatic partial ethers and esters of polyhydroxy alcohols, wherein thealiphatic substituent on the polyhydroxy alcohol contains at least eightcarbon atoms.

17. A compound of the class consisting of boric acid esters, boricacid-sulphuric acid esters, boric acid-phosphoric acid esters, and saltsof said esters, of coconut oil fatty acid monoglycerides.

18. The reaction product obtained by warming a mixture of tallow,glycerine, boric acid and sulphuric acid which contains a sufllcientamount of sulphur trioxide to absorb the water of reaction.

19. A cleansing agent comprising as its essential ingredient a compoundof the class consisting of boric acid esters, boric acid-sulphuric acidesters, boric acid-phosphoric acid esters, and salts of said esters ofat least one aliphatic acid monoglyceride.

20. The product obtained by reacting at least one compound of the classconsisting of partial ethers and esters of polyhydroxy alcohols withboric acid, an aromatic-compound and fuming sulphuric acid.

21. The product prepared by reacting boric acid, an olefin, and at leastone compound of the class consisting of partial ethers and esters ofpolyhydroxy alcohols, with an aromatic compound, and fuming sulphuricacid.

22. The product prepared by reacting boric acid and at least onecompound ,of the class consisting of partial ethers and esters ofpolyhydroxy alcohols with a liquid sulphur dioxide extract of a fractionof petroleum and fuming sulphuric acid.

23. A boric acid ester of a compound of the class consisting of partialethers and sters of polyhydroxy alcohols, the organic substituent on thepolyhydroxy alcohol having at least eight carbon atoms.

24. A boric acid ester of a compound of the.

class consisting of partial ethers and esters of polyhydroxy alcohols,the organic substituent on the polyhydroxy alcohol having at least eightcarbon atoms, and the polyhydroxy alcohol being glycerine.

25. Boric acid esters of monoglycerides of coconut oil fatty acids.

26. A compound of the class consisting of boric acid esters, boricacid-sulphuric acid esters, boric acid-phosphoric acid esters and saltsof said esters, of a partial aliphatic ether of polyhydroxy alcoholswherein the aliphatic substituent on the polyhydroxy alcohol contains atleast eight carbon atoms.

27. An emulsifying agent comprising as the essential ingredient a boricacid ester of a fatty acid monoglyceride.

FRED WEAVER MUNCIE.

